The present study investigates the influence of calcination temperature on the properties and photoactivity of multi-element doped TiO2. The photocatalysts were prepared by incorporating silver (Ag), fluorine (F), nitrogen (N), and tungsten (W) into the TiO2 structure via the sol-gel method. Spectroscopic techniques were used to elucidate the correlation between the structural and optical properties of the doped photocatalyst and its photoactivity. XRD results showed that the mean crystallite size increased for undoped photocatalysts and decreased for the doped photocatalysts when calcination was done at higher temperatures. UV-Vis spectra showed that the absorption cut-off wavelength shifted towards the visible light region for the as-synthesized photocatalysts and band gap narrowing was attributed to multi-element doping and calcination. FTIR spectra results showed the shifting of OH-bending absorption bands towards increasing wave numbers. The activity of the photocatalysts was evaluated in terms of gaseous formaldehyde removal under visible light irradiation. The highest photocatalytic removal of gaseous formaldehyde was found at 88%. The study confirms the effectiveness of multi-element doped TiO2 to remove gaseous formaldehyde in air by visible light photocatalysis and the results have a lot of potential to extend the application to other organic air contaminants.